Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/406—Bright, glossy, shiny surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability

Definitions

• the present invention relates to a film.
• a circuit is provided on the surface of an insulating substrate (polyimide resin, polyphenylene sulfide resin, etc.), and then a cover lay which is a heat resistant resin film having an adhesive layer for the purpose of insulation and circuit protection. Is formed by press lamination through a release film. At this time, the release film is required to have release properties from the printed wiring board material and the press plate, shape followability, uniform formability, transferability of matte appearance, and the like. Further, there is an increasing need for matte films as a base material on which functional layers such as an insulating layer, a hard coat layer, and an electromagnetic wave shielding layer are transferred onto a circuit board surface by a heat press.
• processed products such as a sand matte film, a chemical matte film, and a coating matte film are generally used as the matte film.
• the processed product has a problem of cost increase and quality due to an increase in processes, and improvement has been desired.
• superiority is recognized in a particle-kneaded film produced by a method of extruding a large amount of particles together with a resin, but the particle-kneaded film achieves a high level of low gloss appearance that has recently been required. Is difficult.
• the said particle kneaded film has low light transmittance, when photocuring resin is applied as a functional layer to laminate
• a polyester film containing inorganic particles or organic particles at a high concentration has been proposed as a mat-like transfer substrate used conventionally (for example, Patent Documents 1 and 2). Further, as a film having a high matte appearance, a film in which a resin layer is provided on the surface by coating has been proposed (for example, Patent Document 3).
• Patent Documents 1 and 2 are not designed to ensure transparency, and the variation in surface roughness is not sufficiently reduced. Therefore, when a photocurable resin is applied as a functional layer In addition, there is a problem that the low gloss surface cannot be uniformly transferred.
• the film described in Patent Document 3 has a very low gloss and excellent appearance, but when used for transfer applications, the drop of coarse particles causes problems such as deterioration in the quality of the transfer surface and particle adhesion. There was a case.
• the release layer is provided by coating, the laminated release layer fills the recesses on the film surface, increasing the glossiness, so that the desired matte appearance can be obtained without reducing the glossiness after transfer. There were no challenges.
• the object of the present invention is to eliminate the above-mentioned problems of the prior art.
• An object of the present invention is to provide a film having good processing process suitability that is less likely to cause problems such as particle dropout and slippage.
• the present invention has the following configuration.
• the surface roughness SRa of at least one surface is 100 nm or more and 3000 nm or less, the variation of the surface roughness SRa in the range of 20 cm ⁇ 14 cm is 10% or less, and the parallel line transmittance ST320 of 320 nm is 30% or more.
• a film. (2) The film according to (1), wherein the maximum peak height (SRp) and the maximum valley depth (SRv) of the surface having the surface roughness SRa of 100 nm to 3000 nm satisfy the following formula (II).
• the surface roughness SRa of at least one surface is 100 nm or more and 3000 nm or less, the variation of the surface roughness SRa in the range of 20 cm ⁇ 14 cm is 10% or less, and the parallel line transmittance of 320 nm.
• a film in which ST320 is 30% or more can be mentioned.
• Resin used in the film of the present invention is not particularly limited, for example, polyester such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polyethylene, polypropylene, polyamide, polyimide, polymethylpentene, polychlorinated Vinyl, polystyrene, polymethyl methacrylate, polycarbonate, polyether ether ketone, polysulfone, polyether sulfone, fluororesin, polyetherimide, polyphenylene sulfide, polyurethane, cyclic olefin resin, and the like can be used.
• polyester such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polyethylene, polypropylene, polyamide, polyimide, polymethylpentene, polychlorinated Vinyl, polystyrene, polymethyl me
• polyester a main component from a viewpoint of the handleability of a film, dimensional stability, and economical efficiency at the time of manufacture.
• “having polyester as the main component” means that 50% by mass or more of the resin constituting the film is polyester.
• the film of this invention is a laminated
• polyester is a general term for polymers in which main bonds in the main chain are ester bonds, and can usually be obtained by polycondensation reaction of a dicarboxylic acid component and a glycol component.
• dicarboxylic acid component used here examples include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodiumsulfonedicarboxylic acid.
• oxycarboxylic acid can be exemplified.
• dicarboxylic acid ester derivative components esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, adipic acid
• the components include dimethyl, diethyl maleate, and dimethyl dimer.
• the ratio of terephthalic acid and / or naphthalenedicarboxylic acid in the total dicarboxylic acid component is preferably 95 mol% or more, more preferably 98 mol% or more. From the viewpoint of productivity and productivity.
• the glycol component includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane.
• Diols aliphatic dihydroxy compounds such as 2,2-dimethyl-1,3-propanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyalkylene glycols such as polytetramethylene glycol, 1,4-cyclohexanedimethanol, spiroglycol
• Each component includes aromatic dihydroxy compounds such as alicyclic dihydroxy compounds such as bisphenol A and bisphenol S.
• ethylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, and 1,4-cyclohexanedimethanol are preferably used from the viewpoint of moldability and handleability.
• the proportion of ethylene glycol in all diol components is 65 mol% or more. Two or more of these dicarboxylic acid components and glycol components may be used in combination.
• the film of the present invention needs to have a surface roughness SRa of at least one surface of 100 nm or more and 3000 nm or less from the viewpoint of matte appearance transferability.
• a surface roughness SRa is less than 100 nm, it is difficult to obtain a sufficient matte tone transfer property, and when it is attempted to make the surface roughness larger than 3000 nm, the strength of the film is lowered.
• the surface roughness SRa on at least one side is more preferably 200 nm or more and 2000 nm or more, and most preferably 300 nm or more and 2000 nm or less.
• the method for setting the surface roughness SRa of at least one surface to 100 nm or less is not particularly limited. Examples thereof include a method of containing particles in a high concentration in the film and a method of transferring the shape to the film surface as in embossing.
• the surface roughness SRa of at least one surface is within the above range by the method of incorporating particles in the film at a high concentration, from the viewpoint of achieving both film strength and surface roughness, the base material layer and the particle high concentration content layer ( It is preferable that the particles contained in the A layer have an average particle diameter of 1 ⁇ m or more and 10 ⁇ m or less, and the content thereof is 1% by mass or more and 40% by mass with respect to 100% by mass as a whole.
• the content of particles contained in the A layer is more preferably 3% by mass or more and 35% by mass or less, and most preferably 5% by mass or more and 30% by mass or less.
• the particles contained in the layer A are more preferably an average particle size of 2 ⁇ m or more and 10 ⁇ m or less, further preferably 3 ⁇ m or more and 9 ⁇ m or less, and most preferably 4 ⁇ m or more and 8 ⁇ m or less.
• Both the inorganic particles and the organic particles can be applied to the particles used in the high concentration content (A layer) of the present invention. It is also possible to use inorganic particles and organic particles in combination.
• the inorganic particles and organic particles to be used are not particularly limited.
• silica, aluminum silicate, alumina silicate, calcium carbonate, calcium phosphate, aluminum oxide, mica, clay, talc and the like can be used as the inorganic particles.
• organic particles particles containing styrene, silicone, acrylic acids, methacrylic acids, polyesters, divinyl compounds and the like as constituent components can be used.
• wet and dry silica, colloidal silica, aluminum silicate and the like are preferably used.
• organic particles particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components are preferably used. From the viewpoint of mat appearance and economy, silica, aluminum silicate, and alumina silicate are particularly preferably used. These particles may be used in combination of two or more.
• the film of the present invention needs to have a surface roughness SRa variation of 10% or less in a 20 cm ⁇ 14 cm range with respect to a surface having a surface roughness SRa of 100 nm to 3000 nm.
• the variation of the surface roughness SRa in the present invention is obtained by dividing the sample into 5 cm in the length direction and 4 in the width direction for the sample obtained by cutting the film into a size of 20 cm length ⁇ 14 cm width at any position.
• the surface roughness SRa of 20 samples cut out to a size of 4.0 cm ⁇ width 3.5 cm is calculated by the method described later. If the variation in the surface roughness SRa is larger than 10%, the mat-tone transferability varies, resulting in a poor product appearance.
• the variation in the surface roughness SRa is more preferably 8% or less, and most preferably 6% or less.
• the surface roughness SRa having a certain variation or more has excellent peelability.
• the variation in the surface roughness SRa is preferably 0.1% or more, more preferably 0.5% or more, and further preferably 1% or more.
• the method of setting the variation of the surface roughness SRa in the 20 cm ⁇ 14 cm range of the surface having the surface roughness SRa of 100 nm to 3000 nm in the above range is not particularly limited.
• a layered film having a high-concentration particle-containing layer (A layer), and the layer thickness TA ( ⁇ m) of the A layer and the average particle diameter DA ( ⁇ m) of the particles contained in the A layer satisfy the following formula (I) Is preferably used. 0.8 ⁇ DA / TA ⁇ 10.0 (I)
• the surface roughness SRa can be more uniformly controlled on the surface to some extent, and the variation of the surface roughness SRa can be easily controlled within the above range.
• the film of the present invention is a laminated film having a base material layer and a particle high concentration content layer (A layer)
• the A layer may be disposed only on one surface of the base material layer, and is disposed on both surfaces. It does not matter.
• the functional layer (the surface roughness SRa of the film of the present invention is 100 nm to 3000 nm on the film surface having a surface roughness SRa of the film of the present invention of 100 nm to 3000 nm).
• a transfer material layer for transferring the shape of a certain film surface is provided.
• a photocurable resin is preferably used as the functional layer.
• the film of the present invention needs to have a parallel line transmittance ST320 of 320 nm of 30% or more. When ST320 is less than 30%, the curability of the photocurable resin becomes insufficient, and the property of transferring the mat appearance is deteriorated.
• ST320 is more preferably 45% or more, and most preferably 60% or more. From the viewpoint of handleability of the film, ST320 is preferably 95% or less.
• the transmittance (i) transmittance considering reflection and scattering (total light transmittance measured by collecting transmitted light with an integrating sphere), and (ii) transmission not considering reflection and scattering. Rate (parallel line transmittance for measuring transmittance with parallel rays).
• the variation of ST320 is 10% or less in the range of 20 cm ⁇ 14 cm in order to suppress the variation in matte transferability.
• the variation of ST320 is 10% or less, the curability of the resin when the photocurable resin is applied becomes uniform, and the variation in matte tone transferability can be suppressed.
• the ST320 variation is similar to the above-described evaluation of the variation of the surface roughness SRa. For the sample obtained by cutting the film into a size of 20 cm long ⁇ 14 cm wide at an arbitrary position, it is divided into 5 equal parts in the length direction and in the width direction.
• the sample is divided into four equal parts, cut into a size of 4.0 cm in length and 3.5 cm in width, and each is calculated from the parallel line transmittance ST320 of 320 nm of the sample.
• the ST320 variation in the 20 cm ⁇ 14 cm film range is preferably 8% or less, and most preferably 6% or less.
• the peelability is better when the ST320 has a certain variation or more.
• ST320 variation is preferably 0.5% or more, and more preferably 1% or more.
• the film of the present invention preferably has a film haze of 70% or less.
• a film haze of 70% or less is preferable because the defect inspection property is greatly improved in the structure of the laminate laminated on the material to be transferred.
• a laminated film having a base material layer and a high particle concentration layer (A layer) is used, and the high particle concentration layer (A layer).
• the particle concentration in the base material layer is less than 1% by mass relative to the whole base material layer.
• the particle concentration in the base material layer is preferably less than 0.5% by mass relative to the whole base material layer.
• both the base material layer and the high particle concentration layer (A layer) are made of polyester and used as a biaxially stretched polyester film, generation of voids during stretching of the high particle concentration layer (A layer) described later is suppressed. Therefore, a method of increasing the stretchability of the high-concentration particle content layer (A layer), a method of reducing voids by performing high-temperature treatment in the heat treatment step after stretching described later, and the like are preferably used.
• the particle high-concentration content layer (A layer) contains a copolymerized polyethylene terephthalate resin, a polypropylene terephthalate resin and / or a copolymer thereof, a polybutylene terephthalate resin and / or a copolymer thereof in order to enhance stretchability. It is preferable.
• the method for controlling the variation of ST320 includes adjusting the stretching conditions in the film stretching step.
• the biaxially stretched polyester film is used as the film of the present invention, it is preferable that at least one of the stretching process in the longitudinal direction and the stretching process in the width direction is performed in two or more stages. Even in the case of simultaneous biaxial stretching in the longitudinal direction and the width direction, it is preferable to perform step stretching in two or more stages.
• two or more step stretching means that two or more stretching sections are provided and different stretching conditions are adopted in the two sections.
• the extending section is preferably 2 sections or more and 3 sections or less.
• the film of the present invention in order to make the film haze 70% or less, a method of controlling the amount of particles contained in the film can be mentioned.
• the film of the present invention is a laminated film having a base material layer and a particle high concentration content layer (A layer), the particle content in the base material layer is less than 3% by mass relative to the whole base material layer. It is preferable.
• the film of the present invention has a maximum peak height (SRp) and a maximum valley depth (SRv) of a surface having a surface roughness SRa of 100 nm or more and 3000 nm or less, from the viewpoint of matte tone transferability and film peelability after transfer. It is preferable to satisfy the following formula (II). 1 ⁇ SRp / SRv ⁇ 3 (II) When the maximum peak height (SRp) and maximum valley depth (SRv) on the surface satisfy the formula (II), the transfer peeling from the functional layer is possible while having a ridge shape sufficient to transfer the matte tone. It becomes possible to control the property satisfactorily.
• the maximum peak height (SRp) and the maximum valley depth (SRv) of the surface more preferably satisfy the following formula (II) ′, and most preferably satisfy the formula (II) ′′.
• the method for the maximum peak height (SRp) and the maximum valley depth (SRv) of the surface to satisfy the formula (II) is not particularly limited.
• the film of the present invention is a laminated film having a base material layer and a high-concentration particle content layer (A layer)
• the surface of the film is reduced by a method of reducing the particle diameter of particles contained in the A layer and increasing the particle concentration.
• a method for controlling the shape of the film is preferably used.
• the average particle diameter of the particles contained in the A layer is preferably less than 2.5 ⁇ m, and the content is preferably 3% by mass or more and 40% by mass or less with the entire A layer being 100% by mass.
• the average particle size of the particles contained in the A layer is more preferably less than 2.3 ⁇ m.
• the particle content of the A layer is more preferably 5% by mass or more and 30% by mass or less.
• the film of the present invention has a center area ratio (SSr) of the surface having a surface roughness SRa of 100 nm or more and 3000 nm or less satisfying the following formula (III) from the viewpoint of improving transfer peelability from the functional layer. It is preferable.
• the center area ratio (SSr) is obtained by a measurement method described later, and is an index representing the ratio of the convex reference area in the center plane. When the value is large, it indicates that the protrusions of the protrusions existing on the film surface have a gentle shape, and when the value is small, it indicates that the protrusions existing on the film surface are steep.
• the center area ratio (SSr) of the surface satisfies the formula (III), it is possible to satisfactorily control the transfer peelability from the functional layer while transferring the matte tone to the surface uneven shape.
• the surface area ratio (SSr) of the surface more preferably satisfies the formula (III) ′, and most preferably satisfies the formula (III) ′′.
• the method for satisfying the formula (III) for the center area ratio (SSr) of the surface is not particularly limited.
• the film of the present invention is a laminated film having a base material layer and a high particle concentration layer (A layer)
• the particle size of the particles contained in the A layer is reduced and the particle concentration is increased while the A layer is increased.
• a method of making the thickness of the film constant or less is preferably used.
• the average particle diameter of the particles contained in the A layer is less than 2.5 ⁇ m, the content is 3% by mass to 40% by mass with the entire A layer being 100% by mass, and the lamination thickness of the A layer is less than 3 ⁇ m.
• the ratio of the average particle diameter of the particles contained in the A layer to the layer thickness of the A layer is preferably 0.8 or more and 10 or less, and 1.1 or more and 10 or less. Is more preferable, and 1.3 to 6 is most preferable.
• the thickness change before and after the heat treatment it is preferable to control the thickness change before and after the heat treatment at 100 ° C. for 10 minutes to 0.1% or more and 10% or less.
• a functional layer the surface roughness SRa of the film of the present invention is 100 nm or more and 3000 nm or less on the film surface where the surface roughness SRa of the film of the present invention is 100 nm or more and 3000 nm or less. (Transferable material layer for transferring the shape of a certain film surface) is provided, but a thermal load is applied during the functional layer coating drying when the functional layer is provided.
• the film bites into the functional layer when the functional layer is coated and dried. Becomes smaller, and transfer releasability can be controlled even better.
• the thickness change before and after heat treatment at 100 ° C. for 10 minutes is more preferably 8% or less, and further preferably 6% or less.
• the present inventors diligently studied when the film of the present invention is used as a transfer film, it is more preferable to have a dimensional change in the thickness direction of the film when a thermal load is applied more than a certain value. Revealed that it was excellent.
• the thickness change before and after the heat treatment at 100 ° C. for 10 minutes is preferably 0.5% or more, more preferably 1% or more.
• the surface free energy of the surface having a surface roughness SRa of 100 nm or more and 3000 nm or less is preferably 44 mN / m or less from the viewpoint of transferability.
• the surface free energy on the A layer side is more preferably 42 mN / m or less, and most preferably 15 mN / m or more and 40 mN / m or less.
• the method for bringing the surface free energy of the surface having the surface roughness SRa of the film of the present invention of 100 nm to 3000 nm into the aforementioned range is not particularly limited, but is a release agent such as a silicone compound, a wax compound, or a fluorine compound. And the like, and a method of applying a release coating.
• the film of the present invention is a laminated film having a base material layer and a high particle concentration layer (A layer)
• the release agent may be added to the high particle concentration layer (A layer) or ( A layer)
• a method of applying a release coating to the surface is preferred.
• the thickness of the release coat layer is preferably 0.01 ⁇ m or more and 3 ⁇ m or less, more preferably 0.02 ⁇ m or more and 2 ⁇ m or less, and further preferably 0.03 ⁇ m or more and 1.5 ⁇ m or less.
• Melamine resins that can be used in the present invention include melamine formaldehyde resins, methylated melamine formaldehyde resins, butylated melamine formaldehyde resins, etherified melamine formaldehyde resins, epoxy-modified melamine formaldehyde resins, melamine formaldehyde resins, urea melamine resins, acrylic resins, etc.
• a melamine resin etc. are mentioned. Among them, a melamine formaldehyde resin is preferable, and a methylated melamine formaldehyde resin is particularly preferably used because it has an appropriate release property.
• the mold release layer in this invention contains binder resin other than binder resin and a mold release agent from a viewpoint of film forming property and extending
• a polyester resin, an acrylic resin, and a urethane resin are preferably used, and an acrylic resin is particularly preferably used.
• the acrylic resin include a homopolymer or copolymer of (meth) acrylic acid alkyl ester, a (meth) acrylic acid ester copolymer having a curable functional group at the side chain and / or main chain terminal,
• the curable functional group include a hydroxyl group, a carboxyl group, an epoxy group, and an amino group.
• an acrylic monomer copolymer obtained by copolymerizing an acrylic monomer and an acrylic ester having a curable functional group at the side chain and / or main chain terminal is preferable.
• a mold release agent contained in the mold release layer of this invention a fluorine compound, a long-chain alkyl compound, a wax compound etc. are mentioned, for example. These release agents may be used alone or in combination.
• the fluorine compound that can be used in the present invention is a compound containing a fluorine atom in the compound.
• examples thereof include perfluoroalkyl group-containing compounds, polymers of fluorine-containing olefin compounds, and aromatic fluorine compounds such as fluorobenzene.
• the fluorine compound is preferably a polymer compound.
• the long-chain alkyl compound is a compound having a linear or branched alkyl group having 6 or more carbon atoms, particularly preferably 8 or more.
• Specific examples include, but are not limited to, long-chain alkyl group-containing polyvinyl resins, long-chain alkyl group-containing acrylic resins, long-chain alkyl group-containing polyester resins, long-chain alkyl group-containing amine compounds, long-chain alkyl groups. Examples thereof include a containing ether compound and a long-chain alkyl group-containing quaternary ammonium salt. It is preferable that the long-chain alkyl compound is a polymer compound because the component derived from the release layer on the surface of the counterpart substrate that is bonded when the release film is peeled can be suppressed.
• the wax compound that can be used in the present invention is a wax selected from natural waxes, synthetic waxes, and blended waxes.
• Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, and jojoba oil. Animal waxes include beeswax, lanolin, and whale wax. Examples of the mineral wax include montan wax, ozokerite, and ceresin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum.
• Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, and ketones.
• synthetic hydrocarbons Fischer-Tropsch wax (also known as Sazoir wax) and polyethylene wax are well known, but in addition to these, low molecular weight polymers (specifically, polymers having a viscosity average molecular weight of 500 to 20000) are used. The following polymers are also included. That is, there are polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol block or graft conjugate.
• modified wax examples include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives.
• the derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof.
• Hydrogenated waxes include hardened castor oil and hardened castor oil derivatives.
• the adhesion and release force with the release layer that is laminated and peeled on the release layer can be within an appropriate range.
• the mold release agent a long-chain alkyl compound is preferably used for the purpose of the present invention because the peel force can be adjusted over a wide range.
• polyester resin is used for the base material layer and the particle high concentration content layer (A layer) of the film of the present invention
• each is supplied to a separate extruder and melt extruded.
• the resin temperature is preferably controlled at 255 ° C. to 295 ° C.
• foreign matter is removed and the amount of extrusion is leveled through a filter and a gear pump, and the sheet is coextruded on a cooling drum from a T die to obtain a laminated sheet.
• an electrostatic application method in which a cooling drum and the resin are brought into close contact with each other by static electricity using an electrode applied with a high voltage
• a casting method in which a water film is provided between the casting drum and the extruded polymer sheet, The sheet-like polymer is brought into close contact with the casting drum by a method of adhering the extruded polymer at a glass transition point to (glass transition point ⁇ 20 ° C.) or a combination of these methods, and then solidified by cooling.
• a method of applying an electrostatic force is preferably used from the viewpoint of productivity and flatness.
• the laminated film of the present invention is preferably a biaxially oriented film from the viewpoint of heat resistance and dimensional stability.
• the biaxially oriented film is obtained by stretching an unstretched film in the longitudinal direction and then stretching in the width direction, or by stretching in the width direction and then stretching in the longitudinal direction, or by the longitudinal direction of the film. It can be obtained by stretching by a simultaneous biaxial stretching method in which the width direction is stretched almost simultaneously.
• the stretching ratio in such a stretching method is preferably 2.8 times to 5 times in the longitudinal direction, more preferably 2.9 times to 4.5 times.
• the stretching speed is preferably 1,000% / min or more and 200,000% / min or less.
• stretching temperature of a longitudinal direction shall be 70 degreeC or more and 90 degrees C or less.
• the draw ratio in the width direction is preferably 2.8 times or more and 5 times or less, and more preferably 3 times or more and 4.5 times or less.
• the stretching speed in the width direction is preferably 1,000% / min or more and 200,000% / min or less.
• multilayer film of this invention shall be 2 steps or more of step extending
• the said draw ratio shows a total draw ratio in each direction.
• the film is heat-treated after biaxial stretching.
• the heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. This heat treatment is performed at a temperature not lower than 120 ° C. and not higher than the crystal melting peak temperature of the polyester.
• the heat treatment temperature is preferably set to the melting point ⁇ 20 ° C. or higher and the melting point + 10 ° C. or lower of the high particle concentration layer (A layer), and more preferably set to the melting point ⁇ 10 ° C. preferable.
• the heat treatment time can be arbitrarily set as long as the characteristics are not deteriorated, and is preferably 5 seconds to 60 seconds, more preferably 10 seconds to 40 seconds, and most preferably 15 seconds to 30 seconds.
• the surface of the A layer can be coated with a release layer in-line.
• a method of providing the coating layer in-line in the film manufacturing process at least uniaxially stretched film with a coating layer composition dispersed in water is uniformly applied using a metalling ring bar or gravure roll. And the method of drying a coating material, performing extending
• the thickness of the release layer is preferably 0.02 ⁇ m or more and 0.1 ⁇ m or less.
• various additives such as antioxidants, heat stabilizers, ultraviolet absorbers, infrared absorbers, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, etc. may be added to the release layer. Good.
• a laminated film having a low gloss layer having a glossiness of 30 or less on at least one surface of the base material layer, and the surface roughness SRa of the low gloss layer surface is 100 nm.
• Examples include a laminated film in which the dispersion of the surface roughness SRa in the 20 cm ⁇ 14 cm range of the film is 3000% or less, and the parallel line transmittance ST320 of 320 nm is 30% or more.
• a low gloss appearance can be transferred when used as a transfer film by having a low gloss layer having a glossiness of 30 or less.
• the glossiness of the low gloss layer is more preferably 25 or less, and further preferably 20 or less.
• the glossiness of the low gloss layer can be controlled by adding particles used in the high particle concentration layer (A), adjusting the surface roughness of the low gloss layer, and the like.
• the low gloss layer is more preferably a high particle concentration layer (A).
• the glossiness in this invention represents the 60 degree specular glossiness calculated
• the film of the present invention has a surface roughness SRa of at least one side of 100 nm to 3000 nm, a small variation in the surface roughness SRa in the range of 20 cm ⁇ 14 cm, and a high parallel line transmittance of 320 nm.
• SRa surface roughness
• transfer and shape fixation with a sufficiently low gloss appearance can be achieved. For this reason, in a circuit formation process, it can use suitably as a transfer film excellent in the transferability of the mat-like appearance.
• Polyester composition Polyester resin and film can be dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue component and by-product diethylene glycol can be quantified using 1 H-NMR and 13 C-NMR. it can.
• HFIP hexafluoroisopropanol
• the components constituting each layer can be collected and evaluated by scraping off each layer of the film according to the laminated thickness.
• the composition was computed by calculation from the mixing ratio at the time of film manufacture.
• the laminated film thickness was measured using a dial gauge thickness meter having a flat tip and a diameter of 4 mm (manufactured by Mitutoyo Corporation). The thickness of 5 points at the center of the film, 4 cm position (2 points) in the length direction from the film center, and 4 cm position (2 points) in the width direction was measured, and the average value was taken as the film thickness.
• Di is the equivalent circle diameter of the particles
• N is the number of particles.
• ⁇ Measuring device 3D fine shape measuring instrument (manufactured by Kosaka Laboratory, ET-4000A type)
• Analysis equipment 3D surface roughness analysis system (TDA-31 type) -Stylus: Tip radius 0.5 ⁇ m R, diameter 2 ⁇ m, made of diamond • Needle pressure: 100 ⁇ N ⁇ Measurement direction: film longitudinal direction and film width direction average after each measurement ⁇ X measurement length: 1.0 mm -X feed speed: 0.1 mm / s (measurement speed) ⁇ Y feed pitch: 5 ⁇ m (measurement interval) -Number of Y lines: 81 (measured number) ⁇ Z magnification: 20 times (vertical magnification) ⁇ Low frequency cut-off: 0.20mm High frequency cut-off: R + Wmm (roughness cut-off value) R + W means not cut off.
• Gaussian space type-Leveling Available (tilt correction) - reference area: 1mm 2. Measurement was performed under the above conditions, and thereafter, the center plane average roughness SRa, maximum peak height SRp, maximum valley depth (SRv), and center area ratio (SSr) were calculated using an analysis system.
• a variation film having a surface roughness SRa in the 20 cm ⁇ 14 cm range of the film is cut into a size of 20 cm ⁇ width (parallel to the width direction) 14 cm in length (parallel to the longitudinal direction) as a sample.
• the sample was further divided into 5 equal parts in the length direction and 4 equal parts in the width direction, and cut into a size of 4.0 cm length ⁇ 3.5 cm width (20 samples in total).
• it computed from each surface roughness SRa similarly to (7), and the variation was calculated
• the thickness change was calculated as follows.
• Thickness change (%) ⁇
• Surface free energy Four types of water, ethylene glycol, formamide and diiodomethane were used as measurement solutions, and the film surface of each liquid was measured using a contact angle meter (CA-D type manufactured by Kyowa Interface Science Co., Ltd.). The static contact angle with respect to was determined. Each liquid is measured five times, and the average contact angle ( ⁇ ) and the surface tension component of the measurement liquid (j) are substituted into the following equations, respectively, and simultaneous equations consisting of four equations are expressed as ⁇ L , ⁇ + , Solved for ⁇ ⁇ .
• the film was cut into a length of 20 cm and a width of 14 cm.
• the following release layer forming solution is applied to the surface of the film with an SRa of 100 nm to 3000 nm by gravure coating (if the SRa is 100 nm to 3000 nm on both surfaces, the surface roughness (SRa) is small). And dried in an oven at 180 ° C. for 20 seconds. Further, the coating composition for forming a hard coat layer was applied using a slot die coater while controlling the flow rate so that the thickness after drying was 5 ⁇ m, and dried at 100 ° C. for 1 minute to remove the solvent. A laminate in which the coat layer was laminated was obtained.
• the obtained film / release layer / hard coat layer laminate was heated to a temperature of 160 ° C. for both the upper mold temperature and the lower mold temperature.
• 125 MPa polyimide film (Toray DuPont Kapton 500H / V) /laminate/0.125 mm thickness polyimide film (Toray DuPont Kapton 500H / V) /0.2 mm thick aluminum plate The heating press was performed for 1 hour under these conditions.
• the laminate / polyimide film is taken out and irradiated with 300 mJ / cm 2 ultraviolet rays from the laminate side using a high-pressure mercury lamp to cure the hard coat layer to obtain a sample.
• This sample was subjected to a peel test at the interface between the film and the release layer (film / (this interface) / release layer / hard coat layer), and the peelability was evaluated according to the following criteria.
• Coating composition for forming hard coat layer The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition for forming a hard coat layer having a solid concentration of 40% by mass.
• C could not be peeled.
• the obtained laminate was laminated on a polyimide film (“Kapton” (registered trademark) 500 H / V manufactured by Toray DuPont) at 70 ° C./0.2 MPa, and 800 mJ / cm 2 of ultraviolet light was applied from the laminate side using a high-pressure mercury lamp. Irradiated. At this time, a half of the sample (length 20 cm ⁇ width 7 cm) was subjected to a photomask (the portion subjected to the photomask was not subjected to UV exposure). The peel strength between the film and the photosensitive polyimide layer was measured for each of the UV exposed portion and the UV unexposed portion, and evaluation was performed according to the following criteria.
• Kapton registered trademark 500 H / V manufactured by Toray DuPont
• the peel strength of the laminate of the film / photosensitive polyimide layer was 15 cm long ⁇ 5 cm wide, forcibly peeled between the film and the photosensitive polyimide layer, and a 180 ° peel test was performed using a tensile tester ( Measurement was performed using a Tensilon UCT-100 manufactured by Orientec Co., Ltd. at 25 ° C. and 50% RH atmosphere at a peeling rate of 300 mm / min. In addition, the average value of the intensity
• the peel strength between the film and the photosensitive polyimide layer was measured for each of the UV-exposed part and the UV-exposed part, and evaluated according to the following criteria.
• C The difference in peel strength between the UV-exposed portion and the UV-exposed portion is 1 N / 50 mm or more.
• D Separation was not possible in at least one of the UV-exposed portion and the UV-exposed portion.
• the haze film was cut into a square shape with a side of 10 cm, and haze measurement was performed using a Nippon Denshoku Co., Ltd. haze meter NDH-5000. The measurement was carried out at three locations, and the average value was defined as haze in the present invention.
• the polyester resin used for film formation was prepared as follows.
• Polyethylene terephthalate resin (intrinsic viscosity 0.65) in which the terephthalic component is 100 mol% as the dicarboxylic acid component and the ethylene glycol component is 100 mol% as the glycol component.
• Polyethylene terephthalate resin in which isophthalic acid is copolymerized in an amount of 20 mol% with respect to the dicarboxylic acid component (intrinsic viscosity 0.8).
• Polybutylene terephthalate resin (intrinsic viscosity 1.2) having 100 mol% of terephthalic component as dicarboxylic acid component and 100 mol% of 1,4-butanediol component as glycol component.
• Particle Master E Polyethylene terephthalate particle master (inherent viscosity 0.65) containing polyester A with colloidal silica particles having an average particle diameter of 3 ⁇ m at a particle concentration of 30% by mass.
• Particle Master F Polyethylene terephthalate particle master (inherent viscosity 0.65) containing polyester A with colloidal silica particles having an average particle diameter of 5 ⁇ m at a particle concentration of 30% by mass.
• Particle Master G Polyethylene terephthalate particle master (intrinsic viscosity 0.65) containing polyester silicate alumina particles having an average particle diameter of 3 ⁇ m at a particle concentration of 30% by mass.
• Particle Master H Polyethylene terephthalate particle master (inherent viscosity 0.65) containing polyester silicate alumina particles having an average particle diameter of 5 ⁇ m at a particle concentration of 30% by mass.
• Copolymer emulsion obtained by reaction.
• Particles Obtained by diluting silica particles having a number average particle diameter of 170 nm (“Snowtex” (registered trademark) MP2040 manufactured by Nissan Chemical Industries, Ltd.) with pure water so that the solid content concentration becomes 40% by weight. Water dispersion.
• Example 1 The raw materials are respectively supplied to the extruder so that the composition and lamination ratio are as shown in the table, the extruder cylinder temperature is set to 270 ° C., the short tube temperature is set to 275 ° C., the die temperature is set to 280 ° C., and the resin temperature is 280 ° C. Then, it was discharged in a sheet form onto a cooling drum whose temperature was controlled to 25 ° C. from a T-die. At that time, a wire electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched sheet. Next, the film is stretched in the longitudinal direction at a stretching temperature of 85 ° C.
• the film was stretched at a rate of% / min (total stretching ratio: 3.3 times). Thereafter, a corona discharge treatment was applied, and a release coating solution (aqueous dispersion) was applied to the surface of the A layer side using a metal ring bar so that the wet thickness became 13.5 ⁇ m, and then applied to a tenter type horizontal stretching machine. In the width direction, the film is stretched 1.8 times as the first stage at a stretching temperature of 100 ° C. and stretched at a stretching speed of 30,000% / min.
• Example 2 A film having a film thickness of 25 ⁇ m was obtained in the same manner as in Example 1 except that the composition and lamination ratio were changed as shown in the table.
• Example 3 A film having a film thickness of 16 ⁇ m was obtained in the same manner as in Example 1 except that the composition and lamination ratio were changed as shown in the table.
• Example 4 A film having a film thickness of 25 ⁇ m was obtained in the same manner as in Example 1 except that the composition and lamination ratio were changed as shown in the table.
• Example 6 A film having a film thickness of 16 ⁇ m was obtained in the same manner as in Example 2 except that the stretching condition in the longitudinal direction was 3.3 times stretched at 85 ° C. and the stretching condition in the width direction was stretched 3.6 times at 100 ° C. It was.
• Example 7 A film having a film thickness of 16 ⁇ m was obtained in the same manner as in Example 1 except that the composition and the lamination ratio were changed as shown in the table and the release coating solution was not applied after stretching in the longitudinal direction.
• Example 8 A film having a film thickness of 19.5 ⁇ m was obtained in the same manner as in Example 1 except that the composition, configuration, and lamination ratio were changed as shown in the table, and the release coating solution was not applied after stretching in the longitudinal direction.
• Example 9 The composition and lamination ratio were changed as shown in the table, and the film was stretched 1.6 times as the first stage at a stretching temperature of 85 ° C. in the longitudinal direction, and 2.4 times stretched as the second stage at a stretching temperature of 88 ° C. (total stretching ratio of 3 And 1.9 times as the first step at a stretching temperature of 100 ° C. in the width direction, and 2.2 times stretching (total stretching ratio of 4.2 times) at the second stage at a stretching temperature of 120 ° C.
• a film having a film thickness of 14.5 ⁇ m release coating layer: 0.03 ⁇ m, A layer: 2 ⁇ m, substrate layer: 12.5 ⁇ m
• Example 10 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 11 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 12 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 13 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 14 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 15 A film having a film thickness of 14.5 ⁇ m was obtained in the same manner as in Example 9 except that the composition and lamination ratio were changed as shown in the table.
• Example 16 A film having a film thickness of 9 ⁇ m was obtained in the same manner as in Example 4 except that the composition and lamination ratio were changed as shown in the table.
• Example 17 In the longitudinal direction, the film is stretched 1.7 times as the first stage at a stretching temperature of 85 ° C., and is stretched 2.4 times (total stretching ratio: 4.1 times) as the second stage at a stretching temperature of 88 ° C., and the stretching temperature is 100 in the width direction. Stretched 1.9 times as the first stage at °C, stretched at the stretching temperature of 120 °C, stretched the second stage 2.2 times (total stretching ratio 4.2 times), and then heat-treated at 252 °C in the tenter. A film having a film thickness of 14.5 ⁇ m (release coating layer: 0.03 ⁇ m, A layer: 2 ⁇ m, base material layer: 12.5 ⁇ m) was obtained in the same manner as Example 11 except for the above.
• Example 18 In the longitudinal direction, the film is stretched 1.2 times as the first stage at a stretching temperature of 85 ° C., stretched 1.2 times as the second stage at a stretching temperature of 86 ° C., and 1.6 times as the third stage at a stretching temperature of 87 ° C. It is 1.7 times as the 4th stage at 88 ° C (total draw ratio: 3.9 times), stretched 1.2 times as the 1st stage at 100 ° C in the width direction, and the 2nd stage at 110 ° C.
• Example 11 except that the film was stretched 1.2 times, stretched at a stretching temperature of 115 ° C., stretched at a third stage of 1.6 times, stretched at 120 ° C., stretched at a fourth stage of 1.8 times (total stretch ratio of 4.1 times).
• a film having a film thickness of 14.5 ⁇ m (release coating layer: 0.03 ⁇ m, A layer: 2 ⁇ m, substrate layer: 12.5 ⁇ m) was obtained.
• Example 1 A film having a film thickness of 22.5 ⁇ m was obtained in the same manner as in Example 8 except that the composition and lamination ratio were changed as shown in the table.
• Example 2 A film having a film thickness of 25 ⁇ m was obtained in the same manner as in Example 4 except that the composition and lamination ratio were changed as shown in the table.
• Example 3 A film having a film thickness of 20.5 ⁇ m was obtained in the same manner as in Example 2 except that the composition and lamination ratio were changed as shown in the table.
• a film surface having a surface roughness SRa of 100 nm or more and 3000 nm or less is described as A surface
• a film surface having a surface roughness SRa of 100 nm or more and 3000 nm or less is described as B surface.
• the surface having a large surface roughness is described as A1 surface
• the surface having a low surface roughness SRa is described as A2 surface.
• the film of the present invention has a surface roughness SRa of at least one side of 100 nm to 3000 nm, a small variation in the surface roughness SRa in the range of 20 cm ⁇ 14 cm, and a high parallel line transmittance of 320 nm.
• SRa surface roughness
• transfer and shape fixation with a sufficiently low gloss appearance can be achieved. For this reason, in a circuit formation process, it can use suitably as a transfer film excellent in the transferability of the mat-like appearance.

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